One Component

Figure 4-9. Vapor-liquid equilibria for a binary system where one component dimerizes in the vapor phase. Activity coefficients show only small deviations from liquid-phase ideality.

In general, the final network design should be achieved in the minimum number of units to keep down the capital cost (although this is not the only consideration to keep down the capital cost). To minimize the number of imits in Eq. (7.1), L should be zero and C should be a maximum. Assuming L to be zero in the final design is a reasonable assumption. However, what should be assumed about C Consider the network in Fig. 7.16, which has two components. For there to be two components, the heat duties for streams A and B must exactly balance the duties for streams E and F. Also, the heat duties for streams C and D must exactly balance the duties for streams G and H. Such balemces are likely to be unusual and not easy to predict. The safest assumption for C thus appears to be that there will be one component only, i.e., C = 1. This leads to an important special case when the network has a single component and is loop-free. In this case, ... 

The results of the assessment are documented in an Environmental Impact Statement (EIS), which discusses the beneficial and adverse impacts considered to result from the activity. The report is one component of the information upon which the decision maker ultimately makes a choice. A final decision can be made with due regard being paid to the likely consequences of adopting a particular course of action, and where necessary by introducing appropriate monitoring programs. 

The strict definition of a phase is any homogeneous and physically distinct region that is separated from another such region by a distinct boundary . For example a glass of water with some ice in it contains one component (the water) exhibiting three phases liquid, solid, and gaseous (the water vapour). The most relevant phases in the oil industry are liquids (water and oil), gases (or vapours), and to a lesser extent, solids. 

So far we have considered only a single component. However, reservoir fluids contain a mixture of hundreds of components, which adds to the complexity of the phase behaviour. Now consider the impact of adding one component to the ethane, say n-heptane (C7H.,g). We are now discussing a binary (two component) mixture, and will concentrate on the pressure-temperature phase diagram. 

One component forms an insoluble monolayer, while the other is soluble. 

Surface heterogeneity may merely be a reflection of different types of chemisorption and chemisorption sites, as in the examples of Figs. XVIII-9 and XVIII-10. The presence of various crystal planes, as in powders, leads to heterogeneous adsorption behavior the effect may vary with particle size, as in the case of O2 on Pd [107]. Heterogeneity may be deliberate many catalysts consist of combinations of active surfaces, such as bimetallic alloys. In this last case, the surface properties may be intermediate between those of the pure metals (but one component may be in surface excess as with any solution) or they may be distinctly different. In this last case, one speaks of various effects ensemble, dilution, ligand, and kinetic (see Ref. 108 for details). 

To define the thennodynamic state of a system one must specify fhe values of a minimum number of variables, enough to reproduce the system with all its macroscopic properties. If special forces (surface effecls, external fields—electric, magnetic, gravitational, etc) are absent, or if the bulk properties are insensitive to these forces, e.g. the weak terrestrial magnetic field, it ordinarily suffices—for a one-component system—to specify fliree variables, e.g. fhe femperature T, the pressure p and the number of moles n, or an equivalent set. For example, if the volume of a surface layer is negligible in comparison with the total volume, surface effects usually contribute negligibly to bulk thennodynamic properties. 

Moreover, using the generalized Gibbs-Duhem equations (A2.1.27) for each of the two one-component phases,... 

In this case, whatever n. moles of each species are required to accomplish the A Fare the same n.s that detennine A.S or AH. Note that this general equation includes the special one-component case of equation (A2.1.52). 

When, for a one-component system, one of the two phases in equilibrium is a sufficiently dilute gas, i.e. is at a pressure well below 1 atm, one can obtain a very usefiil approximate equation from equation (A2.1.52). The molar volume of the gas is at least two orders of magnitude larger than that of the liquid or solid, and is very nearly an ideal gas. Then one can write... 

Given this experimental result, it is plausible to assume (and is easily shown by statistical mechanics) that the chemical potential of a substance with partial pressure p. in an ideal-gas mixture is equal to that in the one-component ideal gas at pressure p = p. 

Gas mixtures are subject to the same degree of non-ideality as the one-component ( pure ) gases that were discussed in the previous section. In particular, the second virial coefficient for a gas mixture can be written as a quadratic average... 

Figure A2.3.2 (a) P-V-T surface for a one-component system that contracts on freezing, (b) P-Visothenns in the region of the critical point.

The grand canonical ensemble is a collection of open systems of given chemical potential p, volume V and temperature T, in which the number of particles or the density in each system can fluctuate. It leads to an important expression for the compressibility Kj, of a one-component fluid ... 

The thennodynamic properties are calculated from the ion-ion pair correlation fimctions by generalizing the expressions derived earlier for one-component systems to multicomponent ionic mixtures. For ionic solutions it is also necessary to note that the interionic potentials are solvent averaged ionic potentials of average force ... 

We now turn to a mean-field description of these models, which in the language of the binary alloy is the Bragg-Williams approximation and is equivalent to the Ciirie-Weiss approxunation for the Ising model. Botli these approximations are closely related to the van der Waals description of a one-component fluid, and lead to the same classical critical exponents a = 0, (3 = 1/2, 8 = 3 and y = 1. 

Figure A2.5.1. Schematic phase diagram (pressure p versus temperature 7) for a typical one-component substance. The full lines mark the transitions from one phase to another (g, gas liquid s, solid). The liquid-gas line (the vapour pressure curve) ends at a critical point (c). The dotted line is a constant pressure line. The dashed lines represent metastable extensions of the stable phases.

Figure A2.5.2 shows schematically the behaviour of several thennodynamic fiinctions along a constant-pressure line (shown as a dotted line in Figure A2.5.1 )—the molar Gibbs free energy G(for a one-component system the same as...

Figure A2.5.2. Schematic representation of the behaviour of several thennodynamic fiinctions as a fiinction of temperature T at constant pressure for the one-component substance shown in figure A2.5.1. (The constant-pressure path is shown as a dotted line in figure A2.5.1.) (a) The molar Gibbs free energy Ci, (b) the molar enthalpy n, and (c) the molar heat capacity at constant pressure The fimctions shown are dimensionless...

With a further increase in the temperature the gas composition moves to the right until it reaches v = 1/2 at the phase boundary, at which point all the liquid is gone. (This is called the dew point because, when the gas is cooled, this is the first point at which drops of liquid appear.) An unportant feature of this behaviour is that the transition from liquid to gas occurs gradually over a nonzero range of temperature, unlike the situation shown for a one-component system in figure A2.5.1. Thus the two-phase region is bounded by a dew-point curve and a bubble-point curve. 

Then, since the chemical potential for a one-component system is just p. = (i= A+pV, a reduced chemical potential can be written in tenns of a reduced density p. = p/p ... 

This vanishes at the critical-solution point as does (d p/d k) at the one-component fluid critical point. Thus... 

The field-density concept is especially usefiil in recognizing the parallelism of path in different physical situations. The criterion is the number of densities held constant the number of fields is irrelevant. A path to the critical point that holds only fields constant produces a strong divergence a path with one density held constant yields a weak divergence a path with two or more densities held constant is nondivergent. Thus the compressibility Kj,oi a one-component fluid shows a strong divergence, while Cj in the one-component fluid is comparable to (constant pressure and composition) in the two-component fluid and shows a weak... 

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